Corrosion inhibited grease composition

ABSTRACT

Corrosion and rust inhibitors for lubricating greases are prepared by Friedel-Crafts-catalyzed interpolymerization of a mono-1-alkene, an olefinically unsaturated carboxylic acid (or ester thereof) wherein the olefinic bond is at least 2 carbon atoms away from the carboxyl group and, optionally, a conjugated diene hydrocarbon. Preferably, the mono-1-alkene is normal and has about 14 to 21 carbon atoms, the unsaturated acid has about 10 to 21 carbon atoms and, if the ester is used, is esterified with a lower alkanol, and the diene has 4 to 5 carbon atoms. The corrosion and rust inhibitors for lubricating greases are prepared by condensation of these polymers with an essentially aliphatic polyamine having up to about 11 amino groups, at least one of which is primary, e.g., pentaethylene hexamine.

United States Patent [72] Inventors Donald D. Carlos Crown Point, 1nd.;Robert 11. Jordan, Chicago Heights; Thomas H. Webb, Haul Crest, [11. [21Appl. No. 752,188

22 Filed Aug. 13, 1968 [45] Patented Sept. 28,1971 [73] AssigneeAtlantic Richiield Company [54] CORROSION INHIBITED GREASE COMPOSITION19 Claims, No Drawings [52] US. Cl 252/40.7, 252/421, 252/515 R, 252/392[51] Int. Cl Cl0m 1/54, C09k 3/00 501 Field of Search 252 42.1, 51.5 A,392, 40.7, 51.5 R

[56] References Cited UNITED STATES PATENTS 2,991,249 7/1961 Andress,Jr. et a1. 252/421 X 3,282,970 11/1966 Riggs,.lr.

ABSTRACT: Corrosion and rust inhibitors for lubricating greases areprepared by Friedel-Crafts-catalyzed interpolymerization of amono-l-alkene, an olefinically unsaturated carboxylic acid (or esterthereof) wherein the olefinic bond is at least 2 carbon atoms away fromthe carboxyl group and, optionally, a conjugated diene hydrocarbon.Preferably, the mono-l-alkene is normal and has about 14 to 21 carbonatoms, the unsaturated acid has about 10 to 21 carbon atoms and, if theester is used, is esterified with a lower alkanol, and the diene has 4to 5 carbon atoms. The corrosion and rust inhibitors for lubricatinggreases are prepared by condensation of these polymers with anessentially aliphatic polyamine having up to about 1 1 amino groups, atleast one of which is primary, e.g., pentaethylenc hexamine.

CORROSION INHIBITED GREASE COMPOSITION This invention relates topolymers and to novel corrosion and rust inhibitors for lubricatinggreases formed from the polymers. More specifically, the presentinvention is directed to a Friedel-Crafts-polymerized polymer of anunsaturated monocarboxylic acid (or ester thereof), an alpha-olefin and,optionally, a conjugated diene, and to corrosion and rust inhibitedlubricating greases which contain these polymers.

Metal surfaces in contact with lubricating greases may be corrodedeither by a component present in or formed in the lubricant duringservice, or by an external material. For example, lubricating greasesare susceptible to oxidation to acidic materials, particularly lowmolecular weight organic acids and mineral acids, which materials maycontribute to corrosion of metal surfaces. Moreover, the presence ingreases of water and oxygen, or of water containing certain salts, suchas sea water, can result in rusting or corrosion of the metal.

Corrosion and rust inhibitors have long been utilized in lubricatinggreases to circumvent the corrosion and rust problems. For example, theprior art has utilized such materi als as sulfonates and naphthenates ofvarious metals, amines and amine salts, and metal soaps of long chainfatty acids or other high molecular weight acids. Such materials are,however, often susceptible to oxidation to corrosive or otherwisedeleterious materials, and may also cause other significant problems,such as, for example, a tendency to weaken or break the gel of thegrease.

It has now been found that a grease-compatible, addition polymer ofdefined olefinically unsaturated carboxylic acid or ester, mono-l-alkeneof about 3 to 25, preferably about 14 to 21 carbon atoms, and(optionally) conjugated, diolefinically unsaturated, aliphatichydrocarbon of 4 to 12, preferably 4 to 5, carbon atoms can be reactedwith organic amines to give a grease-compatible polymer producteffective as a corrosion and rust inhibitor.

Generally, the polymers of the present invention will be formed byaddition polymerization of about 15-95, preferably about 20-90, molpercent of the mono-l-alkene, about 3-85, preferably about 5-40, molpercent of the unsaturated acid or ester, and about 70, or even 80, molpercent of the diene hydrocarbon. Often, when it is desired to excludethe diene hydrocarbon, it is preferred that the polymers contain about95-15, more preferably about 90-60, mol percent of the mono-l-alkene andabout 5-85, more preferably about -40, mol percent of the unsaturatedacid or ester. When the inclusion of the diene hydrocarbon is desired,it will often be preferred to prepare polymers of about 92-15, morepreferably about 85-20, mol percent of the alkene, about 3-55, morepreferably about 5-25, mol percent of the unsaturated acid or ester, andabout 5-80, more preferably about 10-70, mol percent of the diene.

The unsaturated acids or esters polymerized with the monol-alkenes toform the novel, base oil-soluble extreme pressure additive of thisinvention are the acids or esters of the formula wherein R is anolefinically unsaturated, substituted or unsubstituted, hydrocarbonradical of 3 to about 25, preferably about 9 to 20, carbon atoms. The Rgroup, which may be substituted with, for example, acetylenic, aromatic,or other noninterfering groups, contains 1 or more, preferably 1 to 2,olefinic bonds. The carboxylic group is separated, however, from theolefinic bond, or bonds, in R by at least 2 aliphatic, includingcycloaliphatic, carbon atoms, preferably at least about 6 or even atleast about 8 of such carbon atoms. That is, while the R group isolefinically unsaturated, the carboxyl carbon atom is, however, attachedto a nonolefinic carbon atom, and preferably the carboxyl carbon atom isat least about 6, or even at least about 8, aliphatic carbon atomsremoved from the first olefinic bond (i.e., at least 5 or 7 carbon atomsremoved from the first olefinic carbon atom). The nonolefinicallyunsaturated carbon-to-carbon 5 chain separating the olefinic bond, orbonds, from the carboxylic group is preferably paraffinic. R in theabove formula is hydrogen or alkyl of 1 to carbon atoms, preferablylower alkyl, say of l to 3 carbon atoms. When R' is alkyl, saltformation of the acid with the catalyst used for the polymerization isprevented, and alcohol which is formed later in the reaction with anorganic amine can often be readily distilled from the product. Examplesof acids which may be used in this polymer are oleic, linoleic,undecylenic, linolenic, ricinoleic, vinyl acetic, etc. The lower alkylesters of these acids, including the glycerides, *may also be employed,especially the methyl esters. Essentially the same polymer products are,of course, formed from the anhydrides of the acids, as well as fromother acid forms, such as the acid amides, which give a condensationtype reaction with the aliphatic polyamine. Thus the acid reactantserves to supply the acyl group,

to the corrosion and rust inhibiting additives.

The mono-l-alkenes employed in the present invention can be representedby the formula V wherein R" and R' are selected from the groupconsisting of hydrogen and alkyl, including cycloalkyl, and the totalnumber of carbon atoms is from about 3 to 25, preferably about 12 to 21,carbon atoms. Preferably, one of R" and R' is hydrogen and the other isa straight chain alkyl to give a normal olefin. The mono-l-alkenes areoften used as a mixture and may contain minor amounts, usually less than10 percent by weight, of other hydrocarbons such as other olefins,diolefins, saturated hydrocarbons and aromatics. The monol alkene may besubstituted with, e.g., halogen, etc., so long as the substituent doesnot interfere with the polymerization or have any other significantdeleterious effect.

The conjugated, diethylenically or diolefinically unsaturated, aliphatichydrocarbons which may be used in making the polymer include thepolymerizable, conjugated, diethylenically unsaturated alkenes havingfrom 4 to 12 carbon atoms, preferably 4 to 5 carbons, e.g., conjugateddiolefins with a terminal double bond such as 1,3-butadiene, isoprene,etc. The diolefin may be substituted with, e.g., halogen, etc., so longas the substituent does not interfere with the polymerization or haveany other significant deleterious effect. An example of a substituted,conjugated diolefin is chloroprene.

The choice of unsaturated acid, conjugated, diethylenically unsaturatedaliphatic hydrocarbon (if employed) and monol alkene, their ratios andthe extent of reaction are such as to give a grease compatible polymer,and usually the total number of carbon atoms in the acid andmono-l-alkene reactants is at least about 12, preferably at least about18. Also, more than one acid, conjugated diethylenically unsaturatedaliphatic hydrocarbon or mono-l-alkene can be used in forming a givenpolymer, and minor amounts of other polymerizable monomers may bepresent.

The polymer employed in preparing the compositions of the presentinvention can be prepared by subjecting the mono-lalkene, thediethylenically unsaturated, conjugated, aliphatic hydrocarbon (ifemployed) and the unsaturated acid or ester to a polymerizationtemperature of about 0 to 50 C., preferably about 0 to 25 C., in thepresence of a strong Friedel-Crafts catalyst, such as aluminum chlorideor boron trifluoride. A preferred catalyst is aluminum chloride, and itis also preferred to add the unsaturated acid or ester, and anyconjugated, diethylenically unsaturated, aliphatic hydrocarbon to beincluded, to the mono-l-alkene. A coeatalyst may also be employed andwill generally be present in an amount of about 0.5 to volumes ofeoeatalyst per volume of acidalpha olefin-diene feed. A suitableeocatalyst may also be a solvent for the Friedel-Crafts catalyst.Examples of appropriate cocatalysts are the lower alkyl halides,especially ethyl chloride, methyl chloride and the like.

The strong Friedel-Crafts catalyst will generally be present in thecocatalyst solution in a concentration of about 0.01 to percent,preferably about 0.5 to 7 percent, by weight, and the amount of theFriedel-Crafts catalyst employed is generally about 0.1 to percent byweight, preferably about 2 to 15 percent by weight, of the polymerformed, over and above that portion of the catalyst if any which reactswith the carboxyl group of the acid. The proportions of reactants(diene, unsaturated acid and mono-l-alkene) to catalyst solutionemployed may often be about 1:2 to 1:10 or even about 7 1:4 to 1:5 molesof reactants per mole of catalyst solution. At least 0.5 mole ofcatalyst is generally used for every mole of acid in the reactantsmixture, when the acid form is reacted. The polymer may be formed bysimultaneous addition of the catalyst solution and the monomers to areaction vessel. The volumetric ratio of catalyst solution to themonomer reactants in a given unit of time is often about 2:1 to about4:1, preferably about 3 to 1.

After the addition of catalyst and reactants has been completed, thepolymerization may be permitted to continue for a short period of time,generally about 5 to 45 minutes, to insure polymerization to a baseoil-soluble copolymer product, for instance, a normally liquid materialwhich may have a kinematic viscosity at 210 F. of, say, about 'up toabout 1,000 centistokes, preferably about to 150 or even up to about 300centistokes. The polymerization reaction can then be quenched using, forinstance, a lower alkanol, e.g., of 1 to 4 carbon atoms, in solution ina lower alkane. The resulting copolymer can be separated from residualcatalyst as by washing with water, alcohol, dilute aqueous caustic soda,hydrochloric acid or other suitable hydrolyzing and washing methods.

The novel corrosion and rust inhibitor of the present invention can beprepared by the condensation reaction of the copolymer of mono-l-alkene,unsaturated acid (or ester) and diene (if employed) with an essentiallyaliphatic polyamine. Suitable polyamines may be represented by thegeneral formula:

wherein R is an alkylene radical of 2 to 14 or more carbon atoms,preferably 2 to about 7 carbon atoms; R is selected from hydrogen andhydrocarbon radicals such as alkyl, including cycloalkyl, and theradicals may have, for instance, 1 to 30 or more carbon atoms,preferably 1 to about 7 carbon atoms; and n is a number from l to about10, preferably about 2 to 6. R may extend between two N-atoms, forinstance, the two to which R is attached, and, in this case, thesenitrogen atoms will have only one other bond for further attachment. TheR and R substituents are preferably saturated, but may be unsaturated,and may be substituted with nondeleterious substituents, especiallylower alkyl. Thus, for imidazoline formation, a 1,2-diumine, one aminegroup of which is primary, can he used; and suitable amines may berepresented by the following general formula:

wherein R is selected from hydrogen and hydrocarbon radicals such asalkyl, as noted above, or is amino alkylof about 30, preferably 1 toabout 7 carbon atoms, and R" is selected from H and alkyl of l to about12 or more carbon atoms, preferably 1 to about 5 carbon atoms. R mayalso be a hydroxy-alkyl, alkoxy-alkyl or aromatic radical.

Thus, useful polyamines include, for instance, monoalkylenediamines,dialkylaminoalkylamines, polyalkylenepolyamines,N-(p-aminoalkyl)piperazines, etc. illustrative of suitable monoalkylenediamines are ethylene diamine, propylene diamine, butylene diamine,octylene diamine, etc. Examples of suitable dialkylaminoalkylamines aredimethylaminoethylamine, dimethylaminopropylamine,dimethylaminobutylamine, diethylaminopropylamine, diethylaminoamylamine,dipropylaminopropylamine, methylpropylaminoamylamine,propylbutylaminoethylamine, etc. Examples of polyallgylenepolyamines arediethylenetriamine, triethylenetetramine, tetraethylenepentamine,hexapropyleneheptamine, tetrabutylene pentamine, polyamine D (a mixtureof aliphatic and cyclic.polyethyleneamines boiling above 340 C. andhaving an average molecular weight nearly the same as pentaethylenehexamine and having as principal components pentaethylene hexamine,symmetrical and unsymmetrical diaminoethyl triaminoethylamine,symmetrical diaminoethyl triethylenetetramine, symmetrical andunsymmetrical diaminoethyl, diaminoethyl piperazine, piperazinoethyltriethylenetetramine, 4-(N-piperazinoethyl) triethylenetetramine,bis-piperazinoethylamine, and aminoethyl (dipiperazinoethane), polyamineH (bottoms from manufacturing tetraethylene pentamine) etc. SuitableN-(B- aminoalkyl) piperazines include N-methyl-N'-(B-aminocthyl)piperazine, N-(B-aminoisopropyl) piperazine, etc.

In the reaction of the copolymer with an organic polyamine to preparethe corrosion and rust inhibitor of the invention, the polyamine isgenerally reacted in an amount sufiieient to provide about 0.1, or evenabout 0.6, to about 14 gram atoms of hydrogen-bonded nitrogen per moleequivalent of carboxyl groups in the polymer; preferably, about 1.5 to 4gram atoms of hydrogen-bonded nitrogen per mole equivalent of carboxylgroups will be provided. By hydrogen-bonded nitrogen is meant nitrogenof a primary or secondary amine group of the polyamine, which nitrogenmay or may not still be bonded to hydrogen after the polyamine iscondensed with the polymer. By carboxyl group" is meant the group whichmay, depending on the monomer employed, be supplied either by acarboxylic acid or ester. Often, to provide the abovenitrogen-to-carboxyl ratio, there will be used about 0.3 to 1.5, or even2, moles of the polyamine per mole equivalent of carboxyl groups in thepolymer. However, a slight excess of amine can be advantageous to insureessentially complete reaction of the carboxyl groups of the polymer andavoid undue cross-linking, and a large excess of amine may be present.if desired.

The condensation reaction is usually conducted at a temperature of about60 to 320 C. depending upon whether amide or imidazoline formation isdesired. Preferably, the reaction temperature for amide formation isabout to 180 C. and that for imidazoline formation is about 200 to 300C. The reaction is conducted to give a base oil-soluble product andoften the reaction takes about 0.25 to 5 hours, preferably about 0.5 to3 hours, and water or alcohol is removed as formed. The resultingcondensation product is compatible with the base greases and ordinarilyhas a kinematic viscosity at F. of from about 1,000 to 20,000,preferably about 3,000 to about 15,000 centistokes, and a kinematicviscosity at 210 F. of at least about 50 to 1,000, preferably about to750, centistokes. The condensation product is added to the lubricatinggreases in minor amounts, usually in the range of about 0.1 to 5 percentor more, preferably about 0.5 to 2 percent, by weight of the grease. Thegrease constituent of our new compositions can be any known greasecovering the entire range of N.L.G.l. classifications. For instance, thethickening component of the grease can be a metal salt or soap of any ofthe fatty'acids having from about to 32 carbon atoms, which acids can besaturated or unsaturated and substituted, as with other polar groups.These acids include palmitic, stearic, oleic, linoleic, ricinoleic, palmoil fatty acids, cottonseed oil fatty acids, hydrogenated fish oil fattyacids, lard oil fatty acids, rape seed oil fatty acids, etc., and theirmixtures. Other acids, the soaps of which can be employed, are thosederived from petroleum such as naphthenic acids, petroleum oil and waxoxidates. The preferred thickeners are the soaps of hydroxy carboxylicacids in which the hydroxyl group is at least 12 carbon atoms removedfrom the carboxyl group, e.g., l2-hydroxy stearic acid and hydrogenatedcastor oil.

Among the salt or soap-forming bases which can be used in preparing thesoap thickeners are the alkali metal bases such as those of lithium,sodium and potassium, and the alkaline earth metal bases such as thoseof barium, calcium and strontium. Mixtures of these soaps can beutilized as well. The soap content of the grease compositions of thepresent invention will usually be a minor amount sufficient to give thedesired grease consistency and will often vary within therange of about5 to percent, most advantageously between about 5 and 15 percent, byweight of the total grease composition.

Greases employed in the present invention can be oil base greases havinga mineral oil or synthetic oil base (e.g., a synthetic diester base suchas di(2-ethylhexyl) adipate). The mineral oils which can be used are ofwide viscosity range, for instance, including those having viscositiesfrom about 50 SUS at 100 F. to about 2,000 SUS at 210 F. The mineral oilcan be highly refined and solvent treated, or otherwise refined, e.g. byhydrogenation, if desired, by known means. Among the synthetic oilbases, which can be employed are polymerized olefins, alkylatedaromatics, silicone polymers, polyalkylene glycols and their partial orcomplete ethers and esters.

Grease compositions to be used in the present invention can be preparedfrom preformed soaps, or the soaps can be formed in situ in agrease-forming base. In general, it is 40 preferred to thicken a basematerial, such as a mineral oil, with a soap formed in situ and thendehydrate and adjust the viscosity and other properties of the grease tothe desired range by incorporating additional base oil.

Materials normally incorporated in lubricating oils to impart specialcharacteristics can also be added to the compositions of this invention.These include extreme pressure agents, antiwear agents, etc. The amountof such additives included in the composition usually ranges from about0.01 weight percent up to about 20 or more weight percent, and ingeneral they can be employed in any amounts desired, provided thecomposition is not unduly deleteriously affected.

The following example is included to further illustrate the presentinvention.

EXAMPLE I 5 To a mixture of oleflns (predominantly normalmono-l-alkenes) of the following approximate composition:

petroleum sulfonic acids, and l0 was added 1,3 butadiene and methyloleate in a mole ratio of alpha-olefin to butadiene to methyl oleate ofl to 3 to 4, based on the average molecular weight (243) of thealpha-olefin mixture. A one liter flask was equipped with a DeanStarlgtrap and two addition funnels. A Dry lee trap was mounted on,theDean Stark trap to remove and condense thevolatile solvent, ethylchloride, used in the polymerization. One funnel was charged with thepolymerization feed, and to the remaining funnel was charged a catalystsolution consisting of 5.2 grams aluminum chloride per 100 ml. of ethylchloride at 12C.

Both the polymerization feed and the catalyst solution were introducedinto the reaction flask simultaneously, the polymerization mixture at arate of 19.6 ml. per minute, the catalyst solution at a rate of 49.4 ml.per minute. The total time for the addition of olefin-linoleic acid andcatalyst solution was 12 minutes and the polymerization mixture wasstirred for an additional l2 minutes. The temperature during thepolymerization was 15.5 C. and 340 ml. of ethyl chloride was trapped outof the polymerization system. Hexane, 400 ml., and 400 ml. ofisopropanol were added to quench the catalyst.

The copolymer was washed three times with water. The polymer wasstripped of solvents and had a KV at 100 F. of 131.7 cs., acid number of38.0 and an iodine number of 32.0.

To a reaction flask was charged 200 grns. of the copolymer made as notedabove and 26 grams tetraethylene-pentamine. The system was purged withnitrogen over a 15 minute period as the temperature was increased to C.The temperature was increased to 270 C. over a 50 minute period and a 19cm. vacuum was applied at 270 C. for a period of minutes to facilitatethe removal of water. The temperature was allowed to reach roomtemperature under this reduced pressure. The polymer analyzed 3.69percent nitrogen. The product was tested as a corrosion and rustinhibitor in a lithium roller bearing grease in the ASTM D-l743 BearingCorrosion Test, in comparison with the base grease itself, and with thebase grease containing commercially available rust inhibitor Amine T,"an imidazoline-tall oil derivative. The results appear below as table I.

1.57 Amine T." I 0.75 a oi product of Example I.

The results in table l indicate that the polymer additive of example iis highly effective as a corrosion and rust inhibitor. in particular, itis apparent from the F. water spray test that the additive of thepresent invention is far superior in water resistance at elevatedtemperatures than either the base grease or the grease with the Amine Trust and corrosion inhibitor. Rust inhibition properties would,consequently, be retained a much longer time for greases formulated withthe additive of the present example.

EXAMPLE ll The same type of reaction equipment is used as in example i.To a mixture of the alpha-olefin feed as in example I are added isopreneand methyl oleate to produce a mole ratio of alphaolefin-isoprene-methyl oleate of 6.05 to 2.05 to 1.00, based on theaverage molecular weight of the alpha-olefin mixture. The samepolymerization equipment is used as in ex- 1 75 ample l. One funnel ischarged with the reactant feed, and to the remaining funnel is charged acatalyst solution consisting of 5.2 grams aluminum chloride per 100 ml.of ethyl chloride. Both the olefin feed and the catalyst solution areintroduced into the reaction flash simultaneously, the olefin mixture ata rate of 20.8 ml. per minute (0.0525 moles per minute alphaolefin,0.0173 moles per minute isoprene, 0.00860 moles per minute methyloleate), the catalyst solution at a rate of 39.5 ml. per minute (0.0154moles per minute aluminum chloride). The total time for addition is 12minutes and the polymerization is continued for an additional 28minutes. The temperature during polymerization is 16 C. and 280 ml. (59percent) of ethyl chloride are trapped out of the polymerization system.Hexane, 400 ml. and 400 ml. of isopropanol are added to quench thecatalyst. The copolymer is washed with water and after topping ofsolvents, has the following properties: KV at 100 F. of 1,190 cs; KV at210 F. of 94.54 cs; lodine number, 30.7; Saponification number, 24.3;Specific gravity, 0.8780.

To a 500 ml. reaction flask are charged 110 grams of the copolymer andgrams of tetraethylene pentamine. The system is purged with nitrogenover a minute period as the temperature is increased to 65 C. Thetemperature is increased to 270 C. over a 25 minute period and a 15 cm.vacuum is applied at 270 C. These conditions are maintained for a periodof 67 minutes, after which the reaction product is allowed to reach roomtemperature under this reduced pressure. The polymer is washed withwater and stripped of solvents. The polymer has the followingproperties: KV at 100 F. of 5,082 cs; KV at 210 F. of 198.85 cs;Specific gravity, 0.8852; Iodine number 28.7; percent Nitrogen, 2.00.

lnfrared detects the SiNbond and determines the structure to be animidazoline with some amide present.

The polymer is tested as corrosion and rust inhibitor as described inexample 1 and the polymeric product of example 11 proves to havesimilarly excellent properties.

EXAMPLE 111 The same type of reaction equipment is used as in example 1.To a mixture of the normal alpha-olefin feed as used in example l areadded isoprene and linoleic acid in a mole ratio of alpha-olefin toisoprene to linoleic acid of 6.65/2.45/1.0, based on the averagemolecular weight (243) of the alphaolefin mixture. The olefin intake ischarged with the olefinlinoleic acid-diethylenically unsaturated alkenefeed, and the catalyst intake is charged with a catalyst solutionconsisting of 5.2 grams aluminum chloride per 100 ml. of ethyl chlorideat 1 2 C.

Both the reactant feed and the catalyst solution are introduced into thereaction flask simultaneously, the olefiniclinoleic acid-diethylenicallyunsaturated alkene-mixture at a rate of 24.2 ml. per minute (0.0615moles per minute C l4-C2 1 alpha-olefin, 0.026 moles per minuteisoprene, 0.00923 moles per minute linoleic acid), the catalyst solutionat a rate of 49 ml. per minute (0.0192 moles per minute aluminumchloride). The total time for the addition is 10 minutes and thepolymerization mixture is stirred for an additional minutes. Thetemperature during the polymerization is 16 C. and 320 ml. (61 percent)of ethyl chloride are trapped out of the polymerization system. Hexane,400 ml., and 400 ml. of isopropanol are added to quench the catalyst.

The copolymer is washed with dilute hydrochloric acid and washed threeadditional times with water. The polymer is stripped of solvents and hada KV at 100 F of 3,603 cs; KV at 210 F. of 199.54 cs; acid number of25.44 and an iodine number of43.9; and a specific gravity of 0.8778.

To a 500 ml. reaction flask are charged 100 grams of the copolymer madeas noted above and 8.0 grams tetraethylenepentamine. The system ispurged with nitrogen over a 15 minute period as the temperature isincreased to 65 C. The temperature is increased to 270 C. over a 20minute period and a 15 cm. vacuum is applied at 270 C. for a period of75 minutes to facilitate the removal of water. The temperature isallowed to reach room temperature under this reduced pressure. Theproduct is washed and stripped of solvents. The polymer has a specificgravity of 0.8933; KV at 100 F., 13,500 cs; KV at 210 F., 550.63 cs;iodine number, 47.4; and 2.51 percent nitrogen. Infrared detects the C=Nbond and confirms the imidazoline ring structure with a trace of amidepresent. The polymer is tested as a corrosion and rust inhibitor a inexample I, with similarly good properties being indicated.

It is claimed:

l. A lubricating grease composition consisting essentially of a majoramount of a base oil of lubricating viscosity and sufficient fatty acidalkaline metal salt to provide a composition of grease consistency and asmall amount, sufficient to enhance the corrosion and rust inhibitingcharacteristics of the grease, of a grease-compatible condensationreaction product of (A) a grease-compatible copolymer fonned by use of astrong Friedel-Crafts catalyst, of about 5 to mole percent of materialhaving the formula:

R--H1OR wherein R is an olefinically unsaturated hydrocarbon radical of3 to about 25 carbon atoms, the carboxyl carbon atom being separatedfrom all olefinic bonds in R by at least 2 aliphatic carbon atoms, and Ris selected from the group consisting of hydrogen and alkyl of 1 to 15carbon atoms, and about 95 to 15 mole percent of mono-l-alkene of 3 to25 carbon atoms, said material and said monol-alkene being selected sothat the total number of carbon atoms in these components is at leastabout 12, and (B) polyamine having the formula:

wherein R is an alkylene radical of 2 to 14 carbon atoms, R is selectedfrom the group consisting of hydrogen and hydrocarbon radicals of 1 to30 carbon atoms, and n is a number from 1 to about 10, said (A) and (B)being reacted in amounts sufficient to provide about 0.1 to 14 gramatoms of hydrogenbonded nitrogen per mole equivalent of carboxyl groupsin (A).

2. The composition of claim 1 wherein the grease is lithiumsoap-thickened mineral lubricating oil.

3. The composition of claim 1 wherein the condensation reaction productis present in amounts of about 0.1 'to 10 percent, by weight of thegrease.

4. The composition of claim 1 wherein the condensation reaction productis present in amounts of about 0.25 to 7.5 percent, by weight of thegrease.

5. A lubricating grease composition consisting essentially of a majoramount of fatty acid alkaline metal salt thickened mineral oil-baselubricating grease and a small amount, sufficient to enhance the rustand corrosion inhibiting characteristics of the grease, of a mineraloil-base-grease-compatible condensation reaction product of (A) agrease-compatible copolymer, formed by use of a strong FriedelCraftscatalyst, of about 10 to 40 mole percent of material having the formula:

wherein R is an olefinically unsaturated hydrocarbon radical of about 9to 20 carbon atoms, the carboxyl carbon atom being separated from allolefinic bonds in R by at least about 6 paraffinic carbon atoms and R'is selected from the group consisting of hydrogen and lower alkyl, andabout to 60 mole percent of normal mono-l-alkene of about 12 to 21carbon atoms, and (B) polyamine having the formula:

wherein R is an alkylene radical of 2 to 7 carbon atoms, R is selectedfrom the group consisting of hydrogen and alkyl radicals of l to about 7carbon atoms, and n is a number from about 2 to 6, said (A) and (B)being reacted in amounts sufficient to provide about 0.6 to 14 gramatoms of hydrogenbonded nitrogen per mole equivalent of carboxyl groupsin (A).

6. The composition of claim 5 wherein R in the polyamine is hydrogen andR in the polyamine has 2 carbon atoms.

7. The composition of claim 6 wherein the material is methyl oleate.

8. The composition of claim 7 wherein component (B) istetraethylenepentamine and said (A) and (B) are reacted in amountssufficient to provide about 0.3 to 2 moles of (B) per mole equivalent ofmethyl oleate in (A).

9. A lubricating grease composition consisting essentially of a majoramount of a lubricating grease and a small amount, sufficient to enhancethe corrosion and rust inhibiting characteristics of the grease, of agrease-compatible condensation reaction product of (A) agrease-compatible copolymer, formed by use of a strong Friedel-Craftscatalyst, of about 3 to 55 mole percent of material having the formula:

wherein R is an olefinically unsaturated hydrocarbon radical of 3 toabout 25 carbon atoms, the carboxyl carbon atom being separated from allolefinic bonds in R by at least 2 aliphatic carbon atoms and R isselected from the group consisting of hydrogen and alkyl of l to 15carbon atoms, about to 80 mole percent of conjugated, diolefmicallyunsaturated, aliphatic hydrocarbon of 4 to 12 carbon atoms and about 92to 15 mole percent of mono-l-alkene of 3 to carbon atoms, said materialand said mono-l-alkene being selected so that the total number of carbonatoms in these components is at least about 12 and (B) polyamine havingthe formula:

wherein R is an alkylene radical of 2 to 14 carbon atoms, R is selectedfrom the group consisting of hydrogen and hydrocarbon radicals of 1 tocarbon atoms, and n is a number from 1 to about 10, said (A) and (B)being reacted in amounts sufficient to provide about 0.1 to 14 gramatoms of hydrogenbonded nitrogen per mole equivalent of carboxyl groupsin (A).

10. The composition of claim 9 wherein the grease is a lithiumsoap-thickened mineral lubricating oil.

11. The composition of claim 9 wherein the condensation reaction productis present in amounts of about 0.1 to 10 per cent, by weight of thegrease.

12. The composition of claim 9 wherein the condensation reaction productis present in amounts of about 0.25 to 7.5 percent, by weight of thegrease.

13. The composition of claim 12 wherein the conjugated, diolefinicallyunsaturated, aliphatic hydrocarbon is butadienel, 3.

14. The composition of claim 13 wherein the material is methyl oleate.

15. A lubricating grease composition consisting essentially ofa majoramount of mineral oil-base lubricating grease and a small amount,sufficient to enhance the corrosion and rust inhibiting characteristicsof the grease, of a grease-compatible condensation reaction product of(A) a grease-compatible copolymer formed by use of a strongFriedel-Crafts Catalyst of about 5 to 25 mole percent of material havingthe formula:

wherein R is an olefinically unsaturated hydrocarbon radical of about 9to 20 carbon atoms, the carboxyl carbon atom being separated from allolefinic bonds in R by at least about 6 paraffmic carbon atoms and R isselected from the group consisting of hydrogen and lower alkyl, about 10to 70 mole percent of conjugated, diolefinically unsaturated, aliphatichydrocarbon of 4 to 5 carbon atoms and about to 20 mole percent ofnormal mono-l-alkene of about 12 to 21 carbon atoms and (B) polyaminehaving the formula:

wherein R is an alkylene radical of2 to about 7 carbon atoms, R isselected from the group consisting of hydrogen and alkyl radicals of lto about 7 carbon atoms, and n is a number from about 2 to 6, said (A)and (B) being reacted in amounts sufficient to provide about 0.6 to 14gram atoms of hydrogenbonded nitrogen per mole equivalent of carboxylgroups in (A).

16. The composition of claim 15 wherein R in the polyamine is hydrogenand R in the polyamine has 2 carbon atoms.

17. The composition of claim 16 wherein the carboxyl group containingmaterial is methyl oleate.

18. The composition of claim 17 wherein component (B) istetraethylenepentamine and said (A) and (B) are reacted in amountssufficient to provide about 0.3 to 2 moles of(B) per mole equivalent ofmethyl oleate in (A)v 19. The composition of claim 18 wherein theconjugated, diolefinically unsaturated, aliphatic hydrocarbon isbutadiene- 1, 3.

2. The composition of claim 1 wherein the grease is lithiumsoap-thickened mineral lubricating oil.
 3. The composition of claim 1wherein the condensation reaction product is present in amounts of about0.1 to 10 percent, by weight of the grease.
 4. The composition of claim1 wherein the condensation reaction product is present in amounts ofabout 0.25 to 7.5 percent, by weight of the grease.
 5. A lubricatinggrease composition consisting essentially of a major amount of fattyacid alkaline metal salt thickened mineral oil-base lubricating greaseand a small amount, sufficient to enhance the rust and corrosioninhibiting characteristics of the grease, of a mineraloil-base-grease-compatible condensation reaction product of (A) agrease-compatible copolymer, formed by use of a strong Friedel-Craftscatalyst, of about 10 to 40 mole percent of material having the formula:wherein R is an olefinically unsaturated hydrocarbon radical of about 9to 20 carbon atoms, the carboxyl carbon atom being separated from allolefinic bonds in R by at least about 6 paraffinic carbon atoms and R''is selected from the group consisting of hydrogen and lower alkyl, andabout 90 to 60 mole percent of normal mono-1-alkene of about 12 to 21carbon atoms, and (B) polyamine having the formula: wherein R'' is analkylene radical of 2 to 7 carbon atoms, R is selected from the groupconsisting of hydrogen and alkyl radicals of 1 to about 7 carbon atoms,and n is a number from about 2 to 6, said (A) and (B) being reacted inamounts sufficient to provide about 0.6 to 14 gram atoms ofhydrogen-bonded nitrogen per mole equivalent of carboxyl groups in (A).6. The composition of claim 5 wherein R in the polyamine is hydrogen andR'' in the polyamine has 2 carbon atoms.
 7. The composition of claim 6wherein the material is methyl oleate.
 8. The composition of claim 7wherein component (B) is tetraethylenepentamine and said (A) and (B) arereacted in amounts sufficient to provide about 0.3 to 2 moles of (B) permole equivalent of methyl oleate in (A).
 9. A lubricating greasecomposition consisting essentially of a major amount of a lubricatinggrease and a small amount, sufficient to enhance the corrosion and rustinhibiting characteristics of the grease, of a grease-compatiblecondensation reaction product of (A) a grease-compatible copolymer,formed by use of a strong Friedel-Crafts catalyst, of about 3 to 55 molepercent of material having the formula: wherein R is an olefinicallyunsaturated hydrocarbon radical of 3 to about 25 carbon atoms, thecarboxyl carbon atom being separated from all olefinic bonds in R by atleast 2 aliphatic carbon atoms and R'' is selected from the groupconsisting of hydrogen and alkyl of 1 to 15 carbon atoms, about 5 to 80mole percent of conjugated, diolefinically unsaturated, aliphatichydrocarbon of 4 to 12 carbon atoms and about 92 to 15 mole percent ofmono-1-alkene of 3 to 25 carbon atoms, said material and saidmono-1-alkene being selected so that the total number of carbon atoms inthese components is at least about 12 and (B) polyamine having theformula: wherein R'' is an alkylene radical of 2 to 14 carbon atoms, Ris selected from the group consisting of hydrogen and hydrocarbonradicals of 1 to 30 carbon atoms, and n is a number from 1 to about 10,said (A) and (B) being reacted in amounts sufficient to provide about0.1 to 14 gram atoms of hydrogen-bonded nitrogen per mole equivalent ofcarboxyl groups in (A).
 10. The composition of claim 9 wherein thegrease is a lithium soap-thickened mineral lubricating oil.
 11. Thecomposition of claim 9 wherein the condensation reaction product ispresent in amounts of about 0.1 to 10 percent, bY weight of the grease.12. The composition of claim 9 wherein the condensation reaction productis present in amounts of about 0.25 to 7.5 percent, by weight of thegrease.
 13. The composition of claim 12 wherein the conjugated,diolefinically unsaturated, aliphatic hydrocarbon is butadiene-1,
 3. 14.The composition of claim 13 wherein the material is methyl oleate.
 15. Alubricating grease composition consisting essentially of a major amountof mineral oil-base lubricating grease and a small amount, sufficient toenhance the corrosion and rust inhibiting characteristics of the grease,of a grease-compatible condensation reaction product of (A) agrease-compatible copolymer formed by use of a strong Friedel-Craftscatalyst of about 5 to 25 mole percent of material having the formula:wherein R is an olefinically unsaturated hydrocarbon radical of about 9to 20 carbon atoms, the carboxyl carbon atom being separated from allolefinic bonds in R by at least about 6 paraffinic carbon atoms and R''is selected from the group consisting of hydrogen and lower alkyl, about10 to 70 mole percent of conjugated, diolefinically unsaturated,aliphatic hydrocarbon of 4 to 5 carbon atoms and about 85 to 20 molepercent of normal mono-1-alkene of about 12 to 21 carbon atoms and (B)polyamine having the formula: wherein R'' is an alkylene radical of 2 toabout 7 carbon atoms, R is selected from the group consisting ofhydrogen and alkyl radicals of 1 to about 7 carbon atoms, and n is anumber from about 2 to 6, said (A) and (B) being reacted in amountssufficient to provide about 0.6 to 14 gram atoms of hydrogen-bondednitrogen per mole equivalent of carboxyl groups in (A).
 16. Thecomposition of claim 15 wherein R in the polyamine is hydrogen and R''in the polyamine has 2 carbon atoms.
 17. The composition of claim 16wherein the carboxyl group containing material is methyl oleate.
 18. Thecomposition of claim 17 wherein component (B) is tetraethylenepentamineand said (A) and (B) are reacted in amounts sufficient to provide about0.3 to 2 moles of (B) per mole equivalent of methyl oleate in (A). 19.The composition of claim 18 wherein the conjugated, diolefinicallyunsaturated, aliphatic hydrocarbon is butadiene-1, 3.